Interaction Of Metal Ions Research Articles

Thermodynamics-based rules of thumb to evaluate the interaction of chelators and kinetically-labile metal ions in blood serum and plasma.

Metal ions play a very important role in nature and their homeostasis is crucial. A lot of metal-related chemical research activities are ongoing that concern metal-based drugs or tools, such as chelation therapy, metal- and metabolite sensors, metallo-drugs and prodrugs, PET and MRI imaging agents, etc. In most of these cases, the applied chelator/ligand (L) or metal-ligand complex (M-L) has at least to pass the blood plasma to reach the target. Hence it is exposed to several metal-binding proteins (mainly serum albumin and transferrin) and to all essential metal ions (zinc, copper, iron, etc.). This holds also for studies in cultured cells when fetal calf serum is used in the medium. There is a risk that the applied compound (L or M-L) in the serum is transformed into a different entity, due to trans-metallation and/or ligand exchange reactions. This depends on the thermodynamics and kinetics. For kinetically-labile complexes, the complex stability with all the ligands and all metal ions present in serum is decisive in evaluating the thermodynamic driving force towards a certain fate of the chelator or metal-ligand complex. To consider that, an integrative view is needed on the stability constants, by taking into account all the metal ions present and all the main proteins to which they are bound, as well as the non-occupied metal binding site in proteins. Only then, a realistic estimation of the complex stability, and hence its potential fate, can be done. This perspective aims to provide a simple approach to estimate the thermodynamic stability of labile metal-ligand complexes in a blood plasma/serum environment. It gives a guideline to obtain an estimation of the plasma and serum complex stability and metal selectivity starting from the chemical stability constants of metal-ligand complexes. Although of high importance, it does not focus on the more complex kinetic aspects of metal-transfer reactions. The perspective should help for a better design of such compounds, to perform test tube assays which are relevant to the conditions in the plasma/serum and to be aware of the importance of ternary complexes, kinetics and competition experiments.

A Tetranuclear Ni(II)-Cubane Cluster Molecule Build by Four µ3-O-Methanolate (MeO) Ligands, Externally Cohesive by Four Unprecedented Bridging µ2-N7,O6-Acyclovirate (acv-H) Anions

Metal ion interactions with nuclei acids and their constituents represent a multi-faceted and growing research field. This contribution deals with molecular recognition between synthetic purine 17 nucleosides and first-row transition metal complexes, with O- and/or N-amino chelators which are able to 18 engage in intra-molecular N-H···(N or O) and O-H···(N or O) interligand interactions. Crystals of these complexes can also display inter-molecular aromatic π-stacking and/or other non-conventional interactions. In this manuscript, we used 2-(2-aminoethoxy)ethanol (2aee) as a potential N,O(e),O(ol)-chelator for nickel(II). However, unexpectedly, the reaction between NiCl2, acyclovir (acv), and 2aee in methanol afforded parallelepiped apple-green crystals of [Ni(acv-H)(MeO)(H2O)]4·8H2O, (1) a tetranuclear molecule with an equimolar Ni(II):µ3-methanolate(1-):µ2-N7,O6-acyclovirate(1-) (acv-H) ratio. The µ2-N7,O6-(acv-H) metal-binding pattern (MBP) is unprecedented in terms of both its anionic and bridging roles. The single-crystal X-ray diffraction structure as well as thermogravimetric analysis and the (FT-IR +Vis-UV) spectra of 1 are reported. Theoretical density functional theory (DFT) calculations are used to analyse the antiparallel π-stacking interactions that govern the formation of self-assembled dimers in the solid state.

Study of Synthesis, Characterization, DFT, and In Vitro Biological Activity of Cu(II), Co(II), and Fe(II) Metal Complexes Based on Heterocyclic Azo Pyrazole Dye Ligand

A new azo dye ligand was synthesized by coupling 5-amino-3-methyl-1-phenylpyrazole with a diazonium ion of 2-amino-1-naphthalene sulfonic acid. Its Co(II), Fe(II), and Cu(II) complexes were also synthesized. This ligand and its complexes were characterized based on elemental analysis, IR, 1H NMR, UV-vis spectra, and thermogravimetric analysis. The data showed that the proposed complexes have an octahedral geometry around the central metal ion. The nonelectrolytic nature of the complexes was confirmed by molar conductance measurement. X-ray powder diffraction indicates that Co(II) and Fe(II) complexes are amorphous in nature, whereas the Cu(II) complex has crystalline and amorphous phases. The bond strength and molecular stability between the interaction of metal ions and the ligand were investigated by density functional theory (DFT). The in vitro antibacterial activity of the ligand and complexes was tested against two Gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus) and two Gram-negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and a fungus (Candida albicans). The Cu(II) complex exhibited a high antimicrobial effect against all tested microorganisms. The DNA fragmentation percentage and cytotoxic activity against human liver cancer cells (HepG2) were evaluated. All tested compounds showed potential anticancer activity, and the Co(II) complex showed better activity results than the other tested compounds, with IC50 = 19.55 μg/mL.

THE SIMULATION OF INTERMOLECULAR INTERACTIONS OF CARBOXYLIC AND AMINE GROUPS WITH CALCIUM CARBONATE

Surface facilities including tubing and valves at the oilfield have been plagued by mineral scale deposits, which are constitute of calcium carbonate (CaCO3). Penta-potassium diethylenetriaminepentaacetic acid salt (DTPA-K5) has a higher affinity for the metal cations complexes during the chelation process. The eight complexing sites (five carboxylate and three amines) empower the metal ion interactions. This work investigated the molecular dynamics simulations between the DTPA-K5 with the calcium carbonate, CaCO3 scale. The interaction was performed through molecular dynamic (MD) simulation using condensed phase optimised molecular potentials for atomistic simulation studies (COMPASS) force field and the Ewald summation method in Material Studio. The simulation trajectory files examined the intermolecular interactions for radial distribution function (RDF). The simulation shows strong DTPA-K5 with calcium interactions, which revealed the metal ion complexes contributing to the chelation process through the reactive carboxylic and amine functional groups, which were O7 == Ca at radius, r, 2.25 Å with g(r) of 10.09 and N1 -- Ca at radius, r, 2.25 Å with g(r) 2.51.

Influence of Pt/Pd state on ceria-based support in CO oxidation

Noble metal (M: Pt, Pd, PtPd) supported on ceria system catalysts were investigated. The oxidized and reduced forms of the active component were examined in CO oxidation. All catalysts become more active after a reduction pretreatment, which shifts the temperature of CO oxidation. Analysis of the data obtained from characterization techniques indicates that the strong interaction of metal ions with the support prevent the reduction of the initial MOx to metallic M. The formation of M−ceria interfaces efficiently boosts the oxygen activation during CO oxidation, leading to the formation of chemisorbed O on M and the regeneration of the ceria lattice oxygen, thus greatly improving the catalytic performance.

Divalent Metal Cation Optical Sensing Using Single-Walled Carbon Nanotube Corona Phase Molecular Recognition.

Colloidal single-walled carbon nanotubes (SWCNTs) offer a promising platform for the nanoscale engineering of molecular recognition. Optical sensors have been recently designed through the modification of noncovalent corona phases (CPs) of SWCNTs through a phenomenon known as corona phase molecular recognition (CoPhMoRe). In CoPhMoRe constructs, DNA CPs are of great interest due to the breadth of the design space and our ability to control these molecules with sequence specificity at scale. Utilizing these constructs for metal ion sensing is a natural extension of this technology due to DNA's well-known coordination chemistry. Additionally, understanding metal ion interactions of these constructs allows for improved sensor design for use in complex aqueous environments. In this work, we study the interactions between a panel of 9 dilute divalent metal cations and 35 DNA CPs under the most controlled experimental conditions for SWCNT optical sensing to date. We found that best practices for the study of colloidal SWCNT analyte responses involve mitigating the effects of ionic strength, dilution kinetics, laser power, and analyte response kinetics. We also discover that SWCNT with DNA CPs generally offers two unique sensing states at pH 6 and 8. The combined set of sensors in this work allowed for the differentiation of Hg2+, Pb2+, Cr2+, and Mn2+. Finally, we implemented Hg2+ sensing in the context of portable detection within fish tissue extract, demonstrating nanomolar level detection.

Detecting metal ions by the color change in perylene diimide radical anion/b-PEI complex

The photophysical properties of the hydrogen bonded complexes consisting of low-barrier hydrogen bond (LBHB) depend on their environmental conditions. However, the stimuli responsive materials based on LBHB are still a challenging problem. Here, we report a novel material system which has a high color response to metal ions based on the position changes of the proton between the two heavy atoms involved in the low barrier hydrogen bond. Perylene diimide radical anion/branched polyethyleneimine hydrogen bonding complex (TFPDI-b-PEI) linked by low-barrier hydrogen bond ([O1-----H1---N1]−1) is obtained. The spectral responses of TFPDI-b-PEI to different metal ions are investigated in DMF and aqueous solutions by UV–Vis spectrophotometry. The results show that TFPDI-b-PEI can recognize Al3+, Ni2+ and Cd2+ by the blue shift of characteristic absorption peak (from 789 nm to 565 nm) and the change of absorbance. In essence, the geometry of LBHB in TFPDI-b-PEI can switch between two types of hydrogen bond ([O1----H1----N1]−1 and [O1-----H1---N1]−1) via adjusting the interaction between the surrounding molecules and amine groups in LBHB by interaction of metal ions with TFPDI-b-PEI. In addition, based on this hydrogen bonding dynamic property, TFPDI-b-PEI exhibits excellent colorimetric sensing performance for Al3+.

The potential of polyethylene microplastics to transport copper in aquatic systems: Adsorption and desorption studies.

Heavy metals and microplastics are two types of general contaminants that can cause significant damage to water systems and organisms. However, the interaction of heavy metal ions with microplastic in aquatic systems received less attention compared with that of organic contaminants. This study aims to explore the interaction of copper (II) ions with microplastic (polyethylene) in aquatic systems. The adsorption experiments were performed by varying several operational parameters including equilibrium pH, initial Cu (II) concentrations, and contact times. The microplastic was characterized using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared. The results confirmed the porous nature of the microplastic surface and the existence of various binding sites. The maximum Cu (II) uptake by microplastic was recorded as 1.23 mg/g at pH5, according to the Langmuir adsorption isotherm. The experimental isotherm data exhibited a good fit to the Toth model, followed by the Langmuir and Freundlich equations, according to the correlation coefficient and %error values. The pseudo-first kinetics equation showed a better fit to copper (II) kinetics data compared with the pseudo-second kinetics equation. Elution of copper (II) ions from copper (II)-loaded microplastic was attempted using several elutants, and the results indicated that 0.01 M HNO3 performed well with elution efficiency over 99.5%. Thus, the elution experiments furnished proof that Cu-loaded microplastic may leach Cu (II) ions under rich acidic conditions, thereby aiding the transport of Cu (II) ions into the digestive tracts of aquatic organisms. PRACTITIONER POINTS: Polyethylene microplastics showed potential to sorb copper ions. The mechanism was electrostatic interaction between microplastics and metal ions. Maximum copper adsorption by microplastic was recorded as 1.23 mg/g. Once desorbed, Cu(II) transferred into the digestive tracts of aquatic organisms.

The remediation efficiency of heavy metal pollutants in water by industrial red mud particle waste

This study aims to treat heavy metal pollutants in water by applying red mud particle waste. An experiment on the static adsorption of heavy metal ions Pb 2 + (or Cd 2 + and Cu 2 + ) by red mud particles was carried out, and the influences of the type of heavy metal ion, ion concentration, pH value, red mud dosage, reaction time, and temperature on adsorption performance were explored. The competitive adsorption mechanisms of various coexisting heavy metal ions by red mud particles were compared. The red mud samples loaded and not loaded with heavy metal ions were detected by zeta potential measurement, scanning electron microscopy, and Fourier transform infrared spectrometry. The adsorption strength of red mud particles for heavy metal ions was ranked in the sequence of Pb 2 + , Cd 2 + , and Cu 2 + , while increasing temperature enhanced their adsorption. When the initial pH values were 4.3, 5.0, and 3.6 for Pb 2 + , Cd 2 + , and Cu 2 + solutions, the removal peaks were 94.5%, 92.8%, and 78.1%, respectively. The preferred order of adsorption for red mud was Pb 2 + , Cd 2 + and then Cu 2 + under the competitive mechanism of binary/ternary systems due to the discrepancy in the functional groups of red mud particles loaded with different heavy metal ions. • A concept for purifying heavy metal pollutants in water using red mud is proposed. • The competitive adsorption mechanism of various heavy metal ions is revealed. • The influence of temperature on the interaction of heavy metal ions and red mud is emphasized. • An adsorption–desorption model with hysteresis is verified by experimental results.

Metal Ion Doping of Alginate-Based Surface Coatings Induces Adipogenesis of Stem Cells.

Metal ions are important effectors of protein and cell functions. Here, polyelectrolyte multilayers (PEMs) made of chitosan (Chi) and alginate (Alg) were doped with different metal ions (Ca2+, Co2+, Cu2+, and Fe3+), which can form bonds with their functional groups. Ca2+ and Fe3+ ions can be deposited in PEM at higher quantities resulting in more positive ζ potentials and also higher water contact angles in the case of Fe3+. An interesting finding was that the exposure of PEM to metal ions decreases the elastic modulus of PEM. Fourier transformed infrared (FTIR) spectroscopy of multilayers provides evidence of interaction of metal ions with the carboxylic groups of Alg but not for hydroxyl and amino groups. The observed changes in wetting and surface potential are partly related to the increased adhesion and proliferation of multipotent C3H10T1/2 fibroblasts in contrast to plain nonadhesive [Chi/Alg] multilayers. Specifically, PEMs doped with Cu2+ and Fe3+ ions greatly promote cell attachment and adipogenic differentiation, which indicates that changes in not only surface properties but also the bioactivity of metal ions play an important role. In conclusion, metal ion-doped multilayer coatings made of alginate and chitosan can promote the differentiation of multipotent cells on implants without the use of other morphogens like growth factors.

Bonding and 13 C-NMR properties of coinage metal tris(ethylene) and tris(norbornene) complexes: Evaluation of the role of relativistic effects from DFT calculations.

The π-complexes of cationic coinage metal ions (Cu(I), Ag(I), Au(I)) provide useful experimental support for understanding fundamental characteristics of bonding and 13 C-NMR patterns of the group 11 triad. Here, we account for the role of relativistic effects on olefin-coinage metal ion interaction for cationic, homoleptic tris-ethylene, and tris-norbornene complexes, [M(η2 -C2 H4 )3 ]+ and [M(η2 -C7 H10 )3 ]+ (M=Cu, Ag, Au), as representative case of studies. The M-(CC) bond strength in the cationic, tris-ethylene complexes is affected sizably for Au and to a lesser extent for Ag and Cu (48.6%, 16.7%, and 4.3%, respectively), owing to the influence on the different stabilizing terms accounting for the interaction energy in the formation of coinage metal cation-π complexes. The bonding elements provided by olefin → M σ-donation and olefin ← M π-backbonding are consequently affected, leading to a lesser covalent interaction going down in the triad if the relativistic effects are ignored. Analysis of the 13 C-NMR tensors provides further understanding of the observed experimental values, where the degree of backbonding charge donation to π2 *-olefin orbital is the main influence on the observed high-field shifts in comparison to the free olefin. This donation is larger for ethylene complexes and lower for norbornene counterparts. However, the bonding energy in the later complexes is slightly stabilized given by the enhancement in the electrostatic character of the interaction. Thus, the theoretical evaluation of metal-alkene bonds, and other metal-bonding situations, benefits from the incorporation of relativistic effects even in lighter counterparts, which have an increasing role going down in the group.

Amidoxime functionalized PVDF-based chelating membranes enable synchronous elimination of heavy metals and organic contaminants from wastewater.

Aiming at the synchronous elimination of heavy metals and organic contaminants from wastewater, the amidoxime functionalized PVDF-based chelating membrane was fabricated in this study. The structure and morphology of the chelating membrane were characterized using infrared spectroscopy (FT-IR), nuclear magnetic resonance spectrometer (NMR) and scanning electron microscopy (SEM). The SEM results show that the chemical modification with amidoxime groups did not damage the structure of the PVDF-based membrane. The chelating membrane has a high removal efficiency for Cu2+ (77.33%) and Pb2+ (79.23%) owing to the chemisorption through coordination bonds. However, the chelating membrane exhibits a low removal efficiency for Cd2+ (29.88%) due to the physical adsorption. The chelating membrane has a high rejection efficiency of BSA (95.17%) and lysozyme (70.09%), which is attributed to the sieving effect and increased hydrophobicity. Furthermore, the membrane performance for simultaneously removing metals and proteins from simulated wastewater was examined. The interaction of metal ions with proteins (BSA and lysozyme) can enhance the ion removal efficiency of the chelated membrane, but decrease the protein rejection efficiency due to the destructive effect. The amidoxime functionalized PVDF-based chelating membrane has a high potential for application in wastewater treatment.

Metal-Ion Interactions with Dodecapeptide Fragments of Human Cationic Antimicrobial Protein LL-37 [hCAP(134-170)

Isothermal titration calorimetry, circular dichroism (CD) techniques, and in silico analysis were used to determine potential metal binding sites in human cationic antimicrobial protein (hCAP) corresponding to overlapping the dodecapeptide sequences of hCAP(134–170) referred to as LL-37. The correct antibacterial action of LL-37 is closely related to its established unique structure. Disturbances in the LL-37 structure (e.g., unwanted presence of metal ions) lead to a radical change in its biological functions. Five fragments of the LL-37 [hCAP(134–170)], namely, hCAP(134–145) (A1), hCAP(140–151) (A2), hCAP(146–157) (A3), hCAP(152–163) (A4), and hCAP(159–170) (A5), were taken into account and their affinity to Mn(II) and Zn(II) ions was rigorously assessed. We prove that only three of the investigated peptides (A1, A2, and A5) are capable of forming thermodynamically stable complexes with metal ions. Additionally, based on density functional theory (DFT) calculations, we propose the most likely coordination modes of metal(II) to peptides as well as discuss the chemical nature of the interactions. Finally, we present the structural features of the strongest binding peptide, hCAP(159–170), responsible for the metal binding. The presented results provide important structural and thermodynamic information to understand the influence of some metal ions on the activity of hCAP(134–170).

REPEATED WASTE OF HUMATIVES INTO PLAIN METALS IN THE PURIFICATION OF WEAKLY ACID WATER, TO CLEAN Cu2+, Pb2+

Destroyed military and industrial facilities have grave consequences not only for the country's economy, but also for the environment and natural resources. At present, humic acids are quite well known and have been sufficiently studied by the natural sorbent. Due to a wide range of functional groups, they perform accumulative, transport, regulatory, protective and physiological functions. The interaction of metal ions with humates does not have a single clear described mechanism. This is facilitated by the complexity and diversity of the structure of humic acids, as well as various reaction conditions in laboratory and natural conditions. Therefore, ways to increase the efficiency of sorption, improve and search for new properties of these substances still remain relevant.
 In this work, the possibilities of reverse bonding of copper and lead ions in slightly acidic aqueous solutions at pH values of 4,4–6,3 are shown. Humic acids were isolated from peat and brown coal, and potassium humates produced in China were also used. In this study, model solutions of copper (II) sulfate and lead (II) acetate were used with a calculated concentration in terms of copper and lead of about 400 and 1000 mg/dm3, respectively. The regeneration of metal humate complexes was carried out by lowering the pH of the medium to 2,1–2,2. The degree of lead sorption was 97–99 % for Pb2+ solutions with a concentration of 216 mg/dm3. Studies have shown the effectiveness of re-use of regenerated humates with a degree of metal release of 85–91 % in relation to the sorbed amount.
 The metal content in the experiment was determined by inductively coupled plasma atomic spectroscopy.
 It was also found that the ratio of the average values of the specific sorption of lead and copper was from 2,8 to 3,1 for various types of humic acids (humates). The proximity of these values with respect to the atomic masses of lead and copper (3,3), in the author's opinion, is associated with the interaction of copper and lead ions with humates in a stoichiometric ratio due to a chemical reaction (reactions). The sorption given in the experiment is described by a linear dependence in the coordinate system: the mass of the sorbed metal (ions) – the mass of humates.

Electrochemical Studies on Interactions of Cu<sup>2+</sup>, Zn<sup>2+</sup> and Cd<sup>2+</sup> with Leucine and Isoleucine

The interaction of some divalent metal ions with leucine (leu) and isoleucine (ile) was studied in aqueous solution. Electrochemical techniques like cyclic voltammetry, chronoamperometry and chronocoulometry were used for this study. The electrochemical study demonstrates that the maximum interaction of each metal ion occurs with two deprotonated ligand. The metal ions exchange electrons quasi-reversibly in presence of the ligands and some sort of chemical reaction may be competing with diffusion process at the electrode surface. The current-time and charge-time response accounts for the adsorption of reactant or product or both at the electrode surface. Dhaka Univ. J. Sci. 69(3): 230-237, 2022 (June)

Expanded Azaporphyrins Consisting of Multiple BODIPY Units: Global Aromaticity and High Affinities Towards Alkali Metal Ions.

The one-pot self-coupling reaction of 3-amino-5-bromo-BODIPY 9 under Buchwald-Hartwig amination conditions gave nitrogen-bridged cyclic BODIPY tetramer 10, pentamer 11, and hexamer 12. Oxidation of 10, 11, and 12 in the presence of alkali metal ions provided 13, 15, and 16, respectively, as the first examples of expanded azaporphyrins possessing more than six pyrrole rings. Curiously, the oxidation even in the absence of alkali metal ions gave the same complexes as a result of spontaneous complexation. 10-12 showed large association constants (104 -106 M-1 ) with K+ and Na+ , but the spontaneous complexations were not observed, indicating the extremely high affinities of 13-16 toward alkali metal ions, which can be ascribed to the multiple and effective ion-dipole interaction of the alkali metal ion with the negatively polarized F atoms of the BF2 walls surrounding the cavity. Importantly, 13, 14, and 15 show diatropic ring currents as a result of global aromaticity.

Expanded Azaporphyrins Consisting of Multiple BODIPY Units: Global Aromaticity and High Affinities Towards Alkali Metal Ions

AbstractThe one‐pot self‐coupling reaction of 3‐amino‐5‐bromo‐BODIPY 9 under Buchwald–Hartwig amination conditions gave nitrogen‐bridged cyclic BODIPY tetramer 10, pentamer 11, and hexamer 12. Oxidation of 10, 11, and 12 in the presence of alkali metal ions provided 13, 15, and 16, respectively, as the first examples of expanded azaporphyrins possessing more than six pyrrole rings. Curiously, the oxidation even in the absence of alkali metal ions gave the same complexes as a result of spontaneous complexation. 10–12 showed large association constants (104–106 M−1) with K+ and Na+, but the spontaneous complexations were not observed, indicating the extremely high affinities of 13–16 toward alkali metal ions, which can be ascribed to the multiple and effective ion–dipole interaction of the alkali metal ion with the negatively polarized F atoms of the BF2 walls surrounding the cavity. Importantly, 13, 14, and 15 show diatropic ring currents as a result of global aromaticity.

Biosorption of uranium by immobilized Nostoc sp. and Scenedesmus sp.: kinetic and equilibrium modeling

Different activities related to uranium mining and nuclear industry may have a negative impact on the environment. Bioremediation of nuclear pollutants using microorganisms is an effective, safe, and economic method. The present study compared the uranium biosorption efficiency of two immobilized algae: Nostoc sp. (cyanophyte) and Scenedesmus sp. (chlorophyte). Effects of metal concentration, contact time, pH, and biosorbent dosage were also studied. The maximum biosorption capacity (60%) by Nostoc sp. was obtained at 300 mg/l uranium solution, 60 min, pH 4.5, and 4.2 g/l algal dosage, whereas Scenedesmus sp. maximally absorbed uranium (65 %) at 150 mg/l uranium solution, 40 min, pH 4.5, and 5.6 g/l of algal dosage. The interaction of metal ions as Na2SO4, FeCl3, CuCl2, NiCl2, CoCl2, CdCl2, and AlCl3 did not support the uranium biosorption by algae. The obtained data was adapted to the linearized form of the Langmuir isotherm model. The experimental qmax values were 130 and 75 mg/g for Nostoc sp. and Scenedesmus sp., respectively. Moreover, the pseudo-second-order kinetic model was more applicable, as the calculated parameters were close to the experimental data. The biosorbents were also characterized by Fourier-transform infrared spectroscopy (ATR-FTIR), energy-dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM) analyses. The results suggest the applicability of algae, in their immobilized form, for recovery and biosorption of uranium from aqueous solution.

A computational study of metal ions interaction with amyloid-β 1–42 peptide structure in hyperpyrexia: Implications for Alzheimer disease

Given the current context of the SARS-CoV-19 pandemic, among the interfering risky factors with the Aβ peptide aggregation in the brains of Alzheimer’s disease (AD) patients can be hyperpyrexia and increased intracranial pressure (ICP). According to our hypothesis on the relationship between hyperpyrexia and cognitive decline in AD, two models of Aβ peptides were used in this study: the structure of AD amyloid beta-peptide and near-atomic resolution fibril structures of the Aβ peptide. Therefore, the binding templates were constructed for Aβ peptide regions able to bind 9 different metal ions. The fragment transformation method was used for the structural comparison between Aβ chains. Molecular dynamics simulation (MDS) was applied using the Nose-Poincare-Anderson equation to generate a theoretically correct NPT (isothermal–isobaric ensemble). The smallest dissimilarities were observed in the case of Cu+ binding potential followed by Co2+, both with similar variation. Structural changes have also occurred as a result of the dynamic simulation. All these changes suggest an aggravating factor in both hyperpyretic and AD conditions. Our findings suggest that elevated temperature and increased intracranial pressure rise the effect of peptide aggregation, by converting α-helix motif to β-sheet and random coil conformation, which are related to the formation of senile plaques in AD brains.

The Role of Side Chains in the Fine-Tuning of the Metal-Binding Ability of Multihistidine Peptides

The systematic studies of copper(II), nickel(II) and zinc(II) ion complexes of protected multihistidine peptides containing amino acids with different side chains (Ac-SarHAH-NH2, Ac-HADH-NH2, Ac-HDAH-NH2, Ac-HXHYH-NH2 X, Y = A, F, D or K, Ac-HXHAHXH-NH2, X = F or D) have provided information about the metal ion and protein interaction and have made it possible to draw conclusions regarding general trends in the coordination of metal complexes of multihistidine peptides. The stability of the metal complexes significantly depends on the position of the histidines and amino acids, which are present in the neighbourhood of the histidine amino acids as well. The most significant effect was observed on peptides containing aspartic acid or phenylalanine. The redox parameters of complexes, however, depend on the number and position of histidines, and the other side chain donor atoms have practically no effect on the electrochemical properties of imidazole-coordinated species. However, the presence of aspartic acid side chains results in a more distorted geometry of amide-coordinated species and increases the reducibility of these complexes.